EP3700964A1 - Improved stabilizer for polyamides - Google Patents
Improved stabilizer for polyamidesInfo
- Publication number
- EP3700964A1 EP3700964A1 EP18795459.9A EP18795459A EP3700964A1 EP 3700964 A1 EP3700964 A1 EP 3700964A1 EP 18795459 A EP18795459 A EP 18795459A EP 3700964 A1 EP3700964 A1 EP 3700964A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nylon
- thermoplastic composition
- polyamide resin
- tin
- oxalate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003381 stabilizer Substances 0.000 title claims description 4
- 239000004952 Polyamide Substances 0.000 title description 7
- 229920002647 polyamide Polymers 0.000 title description 7
- 239000000203 mixture Substances 0.000 claims abstract description 57
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 32
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 25
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 21
- 239000013538 functional additive Substances 0.000 claims abstract description 14
- 239000003365 glass fiber Substances 0.000 claims abstract description 13
- 229920001778 nylon Polymers 0.000 claims description 41
- 239000004677 Nylon Substances 0.000 claims description 38
- 229920002292 Nylon 6 Polymers 0.000 claims description 20
- 229920002859 polyalkenylene Polymers 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 12
- 239000012783 reinforcing fiber Substances 0.000 claims description 8
- 239000012760 heat stabilizer Substances 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 239000004609 Impact Modifier Substances 0.000 claims description 3
- 229920000299 Nylon 12 Polymers 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000012764 mineral filler Substances 0.000 claims description 3
- 229920006114 semi-crystalline semi-aromatic polyamide Polymers 0.000 claims description 3
- 239000004604 Blowing Agent Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000002667 nucleating agent Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 238000003878 thermal aging Methods 0.000 abstract description 6
- 239000011135 tin Substances 0.000 abstract description 3
- -1 poly(2-methylpentamethylene) Polymers 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 239000004594 Masterbatch (MB) Substances 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 229920003245 polyoctenamer Polymers 0.000 description 10
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 239000012744 reinforcing agent Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000005649 metathesis reaction Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920006099 Vestamid® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000003679 aging effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 description 1
- ZPXGNBIFHQKREO-UHFFFAOYSA-N 2-chloroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Cl)=C1 ZPXGNBIFHQKREO-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 description 1
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 description 1
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000531908 Aramides Species 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000012648 alternating copolymerization Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 229920003233 aromatic nylon Polymers 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000008202 granule composition Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920003246 polypentenamer Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
Definitions
- the present invention relates to polyamides having excellent thermal aging resistance and durability.
- Nylon polymer commonly takes the form of pellets or flakes, which can be melted and shaped for use in plastic applications or extruded as fiber for use in yarn applications, such as apparel, carpet, airbags and outdoor gear. Nylon polymers are desirable in many applications due to its outstanding elasticity, dye-fastness and high melting point.
- Nylon resins are often formulated with additives which impart desired properties to the resin in order to make it suitable for other uses. Desired properties include thermal aging resistance and impact resistance. Typically polymer compositions often comprise fillers to modify the mechanical properties of a resin.
- thermoplastic composition that comprises a polyamide resin and a polyhydric alcohol that provides improved thermal aging stability.
- none of these compositions can meet all the application requirements at temperatures of 230° C for 1000 hours or more.
- the present invention relates to a thermoplastic composition that provides improved thermal aging stability.
- the thermoplastic composition comprises a polyamide resin, reinforcing fibers, tin(ll) oxalate and a functional additive. It has been found that a combination of a polyamide resin with tin(ll) oxalate and functional additive produces a superior product demonstrating greater thermal stability than the polyamide resin alone.
- the present invention relates to a thermoplastic composition that provides improved thermal aging stability.
- the thermoplastic composition comprises a polyamide resin, reinforcing fibers, tin(ll) oxalate and a functional additive. It has been found that a combination of a polyamide resin with tin(ll) oxalate and a functional additive produces a superior product demonstrating greater thermal stability than the polyamide resin alone.
- Suitable polyamide resins that may be used for the current invention include any known polyamides in the art. These include aliphatic, semicrystalline, amorphous, aromatic or semiaromatic nylon resins.
- the nylon resins are those prepared from starting materials of essentially a lactam or a diamine, and an aliphatic, semiaromatic or aromatic dicarboxyiic acid.
- Suitable lactams include caprolactam and laurolactam.
- Suitable amines include
- tetramethylenediamine hexamethylenediamine (HMD), 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2, 4-/2,4, 4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine (MXD) and paraxylylenediamine.
- Suitable dicarboxyiic acids such include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid (DDDA).
- nylon homopolymers or copolymers to be derived from those starting materials are used either singly or as their mixtures.
- polyhexamethylenisophthalamide copolymer (nylon 6.6/6.T/6.I).
- polyhexamethyleneterephthalamide/-polyhexamethylenisophthalamide copolymer nylon 6.T/6.I
- polyhexamethyleneterephthalamide/poly(2-methylpentamethylene)terephthalamide copolymer nylon 6.T/M5.T
- polyhexamethylenesebacamide/polycapramide copolymer (nylon 6.T/6.10/6).
- polyhexamethyleneterephthalamide/ polydodecanamide/ polyhexamethylenadipamide copolymer (nylon 6.T/12/6.6), polyhexamethyleneterephthalamide/polydodecanamide/
- polyhexamethylenisophthalamide copolymer (nylon 6.T/12/6.I), poly m-xylylenadipamide (nylon MXD.6), semicrystalline polyphthalamide (6.T. 6.1, 6.6) as well as their mixtures and copolymers, etc.
- Nylon resins suitable for the current invention are Nylon 6, Nylon 6.6, Nylon 6.12, Nylon 4.6, Nylon 6.10, Nylon 7, Nylon 10, Nylon 10.10, Nylon 12, Nylon 12.12, Nylon 6.T. Nylon 9.T. Nylon 10.T, Nylon 6.T/6.I, Nylon 6.T/DT, Nylon MXD.6 and combinations or copolymers thereof.
- the polyamide resin comprises Nylon 6.6.
- the polyamide resin is semicrystalline polyphthalamide (6.T, 6.I. 6.6). like for example (VESTAMID® Tplus M1000, trademark of Evonik Industries AG).
- Suitable reinforcing fibers that preferably be used for the current invention include any known reinforcing fibers in the art.
- the reinforcing agent that can be used in the process according to the invention, and in the composition obtainable by said process, may be any type of non-metallic fibrous reinforcing agent suitable for use in fiber reinforced thermoplastic compositions for use in high temperature applications.
- a fibrous reinforcing agent is considered herein to be a material having length, width and thickness, wherein the average length is significantly larger than both the width and thickness. Generally, such a material has an aspect ratio UD, defined as the average ratio of the length (L), and the largest of the width and thickness (D) of at least 5.
- the aspect ratio of the fibrous reinforcing agent is at least 10, more preferably at least 20, still more preferably at least 50.
- Suitable non-metallic fibrous reinforcing agents that can be used in the process according to the invention, and in the composition obtainable with said process, are, for example, glass fibers, carbon or graphite fibers, aramide fibers, cellulosic fibers, ceramic fibers, mineral fibers, such as wollastonite, and whiskers.
- glass fibers are chosen.
- the thermoplastic compositions of the current invention may also comprise a functional additive.
- a functional additive is defined with characteristics of flow aid, lubricant, impact modifier, reactive component, or all the properties together.
- Suitable functional additive include a maleic anhydride functionalized elastomeric ethylene copolymer, a maleic anhydride functionalized elastomeric ethylene/propylene copolymer, a terpolymer of ethylene, acrylic ester and maleic anhydride, a maleic anhydride grafted (MAH) polyolefin elastomer or combinations thereof.
- the degree of polymerization is generally from 6 to 2000, preferably from 15 to 1500 and particularly preferably from 25 to 1200.
- suitable polymers are polypentenylene, polyhexenylene, polyheptenylene, polyoctenylene, polynonenylene, polydecenylene, po!y(3-methyk>ctenylene), poly(3-methyldecenylene), polyundecenylene or polydodecenylene.
- Polyalkenylenes are sometimes also termed
- polypentenamer polyhexenamer, polyheptenamer, polyoctenamer etc.
- Polyhexenylene is produced by alternating copolymerization of butadiene and ethene.
- Polyheptenylene is produced by metathesis of cycloheptene (US 4,334,048) and polyoctenylene is produced by metathesis of cycloctene (A. Draxler, Kautschuk + Kunststoff 1981 , pages 185 to 190).
- the higher polyalkenylenes are produced correspondingly.
- mixed polyalkenylenes i.e. copolymers (US 3,974,092: US 3,974,094) or a mixture of various polyalkenylenes can also be used.
- the polyamide resin content of the disclosed compositions preferably ranges from 30% to 99.9% by weight, 35% to 95%, 40% to 90%, 45% to 85%, 50% to 80%, 55% to 75%, particularly 60% to 70% based on total weight of the composition.
- the reinforcing fiber content of the disclosed compositions preferably ranges from 0% to 70% by weight. 5% to 65%, 10% to 60%. 15% to 55%, 20% to 50%, 25% to 45%, particularly 30% to 40% based on total weight of the composition.
- the tin(ll) oxalate content of the disclosed compositions preferably ranges from 0.01 % to 10% by weight, 0.05% to 9%, 0.08% to 8%, 0.1 % to 7%, 0.15% to 6%, 0.2% to 5%, 0.3% to 6%. 0.4% to 5%, 0.5% to 4%, particularly 0.6% to 4% based on total weight of the composition.
- the functional additive content of the disclosed compositions preferably ranges from 0.1 % to 20% by weight, 0.5% to 18%, 1 % to 15%, 3% to 13%, particularly 5% to 10%, based on total weight of the composition.
- the thermoplastic compositions of the current invention may further comprise additives such as lubricants, glass fillers, mineral fillers, plasticizers, pigments, dyes, antioxidants, heat stabilizers, hydrolysis stabilizers, nucleating agents, flame retardants, synergists, drip suppressants, blowing agents, foaming agent and combinations thereof.
- Suitable mineral fillers can be selected from the group consisting of kaolin, clay, talc, and wollastonite, diatom ite, titanium dioxide, mica, amorphous silica and combinations thereof.
- the lubricant may be a metal stearate, ethylene bis-stearamide or any other suitable lubricant.
- Suitable glass fillers are selected from the group consisting of glass fiber, glass flakes, glass beads and combinations thereof.
- the glass fibers may also be coated with a sizing composition and organosilane coupling agents to provide hydrolysis resistance. Suitable coated glass fibers are taught in U.S. Pat. Nos. 6,207,737, 6,846,855, 7,419,721 and 7,732.047, which are herein incorporated by reference.
- Suitable heat stabilizers are selected from the group consisting of hindered phenols, amine antioxidants, hindered amine light stabilizers (HALS), aryl amines, phosphorus based antioxidants, copper heat stabilizers, polyhydric alcohols,
- tripentaerythritol dipentaerythritol, pentaerythritol and combinations thereof.
- the process according to the invention can be carried out by any known melt-mixing process that is suitable for preparing fiber-reinforced thermoplastic molding compositions. Such a process is typically carried out by heating the thermoplastic polymer above the melting temperature or in case the thermoplastic polymer is an amorphous polymer above the glass transition temperature, of the thermoplastic polymer thereby forming a melt of the thermoplastic polymer.
- melt-mixing apparatus for which any melt-mixing apparatus known to one skilled in the art of preparing polymer compositions by melt mixing can be used.
- Suitable melt-mixing apparatus are, for example, kneaders, Banburry mixers, single-screw extruders and twin-screw extruders.
- the constituting components for forming the composition are fed to the melt-mixing apparatus and melt-mixed in that apparatus.
- the constituting components may be fed simultaneously as a powder mixture or granule mixture, also known as dry-blend, or may be fed separately.
- the process according to the invention is not limited in the way the tin(ll) oxalate is added. It may be added, for example, as a powder, a dry-blend or premix comprising the thermoplastic polymer in granulate form and the tin(ll) oxalate in powder form, or as a masterbatch of finely dispersed elementary particles in a carrier polymer.
- the tin(ll) oxalate and polyalkenylene are added in the form of a masterbatch. since this allows a better control of the dosing accuracy of the polyalkenylene and tin(ll) oxalate when the polyalkenylene and tin(ll) oxalate is added in small quantities relative to the thermoplastic polymer.
- Another advantage of the use of a masterbatch is that it is easier to obtain a homogenous blend of the polyalkenylene and tin(ll) oxalate with the thermoplastic polymer.
- the masterbatch may further comprise a binder, lubricant, colorant, fillers, flame retardant component, or other additives.
- the masterbatch comprises the polyalkenylene component and the tin (II) oxalate in a weight ratio from 9 - 6 (polyalkenylene) to 1 - 4 (tin salt) where the sum of these two components is 10, more preferably from about 8 to 2.
- Another embodiment of the current invention comprises a process for molding a shaped article formed from a polyamide resin and the masterbatch composition described above. The process comprises the steps of intimately admixing or combining a granular polyamide resin with the masterbatch composition to form a compounded thermoplastic composition, wherein the masterbatch composition comprises from about 0.05% to about 20% by weight of the compounded thermoplastic composition and then molding the compounded thermoplastic composition into a shaped article.
- the compounded thermoplastic composition produced by the process may be used to make shaped articles via injection molding, extrusion, or cast setting.
- Thermoplastic compositions of the current invention have been found to meet desired heat aging standards.
- the compounded polyamide composition is capable of retaining greater than 60% of its tensile strength (stress at break) after 500 hours of hot air treatment (ISO 2578) compared to the tensile strength before the temperature aging.
- the compounded polyamide composition is capable of retaining greater than 60% of its tensile strength.
- CHOPVANTAGE HP 3610 chopped glass fiber available from PPG Fiber Glass A masterbatch of 80% by weight polyalkenylene (VESTENAMER® 8012, trademark of Evonik) and 20% by weight tin(ll) oxalate was used. Tin(ll) oxalate was commercially available from SIGMA-ALDRICH.
- VESTENAMER® 8012 Polyalkenylene under the trade name VESTENAMER® 8012 was commercially available from EVONIK INDUSTRIES AG.
- Formulations were prepared by melt blending semicrystaiiine polyphthaiamide and the masterbatch of polyalkenylene and tin(ll) oxalate in a 27 mm twin screw extruder.
- the extruder was maintained at about 320° C. with a screw speed of about 300 rpm, and a throughput of 20 kg/hour.
- the glass fibers were added to the melt through a screw side feeder and the compounded mixture was extruded in the form of strands, cooled in a water bath, chopped into pellets, dried at 120° C. for 16 hours.
- the pellets were tested for moisture content level of 0.1 % and then injection molded as standard ISO tensile bars.
- the tensile strength and elongation at break were measured according to ISO 527. The tests were performed using injection molded ISO tensile bars. The hot air aging tests were performed by according to the ISO 2578 testing method. Samples were heat aged in re-circulating air ovens to simulate aging conditions. At specific intervals of heat aging, the samples were removed from the oven and allowed to cool in a temperature and humidity controlled room. Finally, the aged samples and corresponding controls were conditioned for 16 hours before tested for mechanical and thermal properties. Table 1
- Table 1 shows the results of resins with varying amounts of the master batch of polyalkenylene (VESTENAMER® 8012) and tin(ll) oxalate.
- the samples where tested for heat aging at 230° C for 0 hr, 500 hrs, and 1000 hrs.
- Comparison of C1 with Ex1 shows the positive influence of VESTENAMER® 8012/tin(ll) oxalate with respect to heat aging.
- Comparison of C2 with Ex2 to Ex4 shows the positive influence of VESTENAMER® 8012/tin(ll) oxalate with respect to heat aging.
- VESTENAMER® 8012 also acts like an impact modifier. As the content of VESTENAMER® 8012 increases the stress at break decreases.
Abstract
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US15/794,811 US10995188B2 (en) | 2017-10-26 | 2017-10-26 | Stabilizer for polyamides |
PCT/EP2018/079130 WO2019081566A1 (en) | 2017-10-26 | 2018-10-24 | Improved stabilizer for polyamides |
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CN112876841B (en) * | 2021-01-15 | 2022-09-20 | 万华化学(四川)有限公司 | Halogen-free flame-retardant long glass fiber reinforced nylon 12 material with high RTI value as well as preparation method and application thereof |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3607853A (en) | 1969-10-09 | 1971-09-21 | Bayer Ag | Process for the preparation of trans-polypentenamer |
US3974092A (en) | 1970-06-06 | 1976-08-10 | Chemische Werke Huls Aktiengesellschaft | Catalyst for the preparation of polyalkenamers |
US3974094A (en) | 1970-06-11 | 1976-08-10 | Chemische Werke Huls Aktiengesellschaft | Catalyst system for the production of polyalkenamers |
US4298518A (en) * | 1976-09-06 | 1981-11-03 | Mitsubishi Chemical Industries, Ltd. | Polyamide resin composition |
US4346194A (en) | 1980-01-22 | 1982-08-24 | E. I. Du Pont De Nemours And Company | Toughened polyamide blends |
US4334048A (en) | 1981-05-26 | 1982-06-08 | The United States Of America As Represented By The Secretary Of The Navy | Olefin metathesis |
US4417031A (en) | 1982-01-07 | 1983-11-22 | Allied Corporation | Process for preparing graft and block copolymers |
JPS62205156A (en) * | 1986-03-04 | 1987-09-09 | Daiseru Hiyurusu Kk | Resin composition |
DE3613528A1 (en) * | 1986-04-22 | 1987-10-29 | Huels Chemische Werke Ag | IMPACT TOOL POLYAMIDE MOLDS |
DE3935466A1 (en) | 1989-10-25 | 1991-05-02 | Huels Chemische Werke Ag | METHOD FOR PRODUCING A THERMOPLASTICALLY PROCESSABLE, AROMATIC POLYAMIDE |
DE4112668A1 (en) * | 1991-04-18 | 1992-10-22 | Huels Chemische Werke Ag | THERMOPLASTIC MULTILAYER COMPOSITION |
US6207737B1 (en) | 1994-03-14 | 2001-03-27 | Ppg Industries Ohio, Inc. | Glass fiber sizing, sized glass fibers and polyolefin reinforced articles |
DE19513940A1 (en) * | 1994-07-14 | 1996-01-18 | Inventa Ag | Process for the production of precondensates of partially crystalline or amorphous, thermoplastically processable partially aromatic polyamides or copolyamides |
JPH0987454A (en) * | 1995-09-20 | 1997-03-31 | Dainippon Ink & Chem Inc | Thermoplastic resin composition, molding material using the same and molded product |
DE19537365C1 (en) * | 1995-10-06 | 1996-12-19 | Fraunhofer Ges Forschung | Stabilising melt viscosity of polyester |
DE10030716A1 (en) | 2000-06-23 | 2002-01-03 | Degussa | Low temperature impact resistant polymer alloy |
US6846855B2 (en) | 2001-05-01 | 2005-01-25 | Owens Corning Fiberglas Technology, Inc. | Sized reinforcements, and materials reinforced with such reinforcements |
US7732047B2 (en) | 2001-05-01 | 2010-06-08 | Ocv Intellectual Capital, Llc | Fiber size, sized reinforcements, and articles reinforced with sized reinforcements |
JP2002326298A (en) * | 2001-05-02 | 2002-11-12 | Nissan Motor Co Ltd | Heat insulating composite material and seat for car using the same |
EP1498445A1 (en) | 2003-07-18 | 2005-01-19 | DSM IP Assets B.V. | Heat stabilized moulding composition |
US7419721B2 (en) | 2003-12-19 | 2008-09-02 | Ppg Industries Ohio, Inc. | Sizing composition and glass fiber reinforced thermoplastic resin |
DE102004059241A1 (en) | 2004-12-08 | 2006-06-14 | Basf Ag | Impact-modified thermoplastic molding compositions based on vinylaromatic copolymers and polyamide |
CN101432370B (en) | 2006-04-28 | 2012-06-13 | 可乐丽股份有限公司 | Oxygen-absorbing resin composition |
EP2742097A2 (en) | 2011-08-31 | 2014-06-18 | Invista Technologies S.à.r.l. | Compositions of polyhydric alcohols and polyamides |
EP2641932A1 (en) | 2012-03-21 | 2013-09-25 | LANXESS Deutschland GmbH | Thermoplastic moulding compositions |
EP2746046A1 (en) | 2012-12-21 | 2014-06-25 | LANXESS Deutschland GmbH | Composite part |
GB201314880D0 (en) * | 2013-08-20 | 2013-10-02 | C G I Internat Ltd | Fire resistant glazing unit |
CN103665857B (en) * | 2013-11-11 | 2016-07-06 | 青岛康威化纤有限公司 | A kind of fiber-glass reinforced polyethylene alcohol-nylon66 fiber alloy material |
-
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